Silver halide photographic material containing a hydroxyazaidene and a carboxyl substituted 1,2-dithiolane as stabilizing combination

ABSTRACT

A silver halide emulsion layer in a photographic material which contains at least one triazaindene, tetrazaindene or a pentazaindene having at least one hydroxy group and at least one compound having a 1,2-dithiolane or a 1,2-dithiane ring exhibits lower fogging but substantially no reduction in desirable photographic characteristics.

United States Patent [191 Jan.7, 1975 Kondo etal.

[73] Assignee: Fuji Photo Film Co. Ltd.,

Kanagawa, Japan [22] Filed: Mar. 23, 1973 [21] Appl. No.: 344,399

[30] Foreign Application Priority Data Mar. 29, 1972 Japan 47-31434 [52] US. Cl 96/107, 96/108, 96/109 [51] Int. Cl G03c 1/28, G03c 1/34 [58] Field of Search 96/107, 108, 109

[56] References Cited UNITED STATES PATENTS 2,728,668 l2/l955 Mochel 96/l(l9 2,948,614 8/1960 Allen et al. 96/109 3,128,186 4/1964 Corben et al. 96/l09 3,732,104 5/l973 Vandenabeele et al. 96/l09 Primary Examiner-Norman G. Torchin Assistant Examiner-Won H. Louie, Jr.

Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A silver halide emulsion layer in a photographic material which contains at least one triazaindene, tetrazaindene or a pentazaindene having at least one hydroxy group and at least one compound having 21 L2- dithiolane or a l,2-dithiane ring exhibits lower fogging but substantially no reduction in desirable photographic characteristics.

15 Claims, N0 Drawings SILVER IIALIDE PHOTOGRAPHIC MATERIAL CONTAINING A I-IYDROXYAZAIDENE AND A CARBOXYL SUBSTITUTED l,2-DITIIIOLANE AS STABILIZING COMBINATION BACKGROUND OF THE INVENTION ide emulsion, there have been known sulfur sensitization, noble metal sensitization, reduction sensitization, sensitization with a selenium compound and the like. These sensitizing methods are usually referred to as chemical sensitizations. The sensitizing method with alkylene oxide or polyalkylene glycols is also well known. It is further known to suitably combine two or more of these sensitizing methods to thereby obtain a required photographic sensitivity.

However, when these sensitizing methods are employed, fogging is liable to increase though there is recognized a remarkable increase in photographic sensitivity. Therefore, it is necessary to lower such fogging. A number of compounds have been suggested for this purpose.

Such compounds are, in general, called anti-fogging agents among those skilled in the art and, in some cases, are referred to as stabilizing agents." These so called anti-fogging agents have the common property of lowering the fogging of photographic emulsions but, at the same time, possess the defect of reducing photographic sensitivity or other photographic characteristics, e.g., gamma. Accordingly, the anti-fogging agents have so far been used with some unavoidable loss of sensitivity. Therefore, a method to lower the fogging alone while maintaining the inherent photographic sensitivity has been eagerly sought.

SUMMARY OF THE INVENTION A primary object of the present invention is to provide a silver halide photographic light-sensitive material wherein fogging is sufficiently lowered without a reduction in sensitivity.

Another object of the invention is to provide a silver halide photographic light-sensitive material wherein the increase in fogging during storage is lowered.

A further object of the invention is to provide a silver halide photographic light-sensitive material undergoing less variations in sensitivity or gamma value during storage.

Compounds having a 1,2-dithiolane ring or a 1,2- dithiane ring are known as an anti-fogging agent for silver halide photographic emulsions. However, while these compounds depress fogging, they have the defect that, similarly to other anti-fogging agents, they degrade sensitivity and other photographic characteristies. The inventors have now found that the defects of the compounds having a 1,2-dithiolane ring or a 1,2- dithiane ring, such as a reduction in sensitivity, can be removed by the combined use of such compounds and one or more azaindenes.

This fact is quite surprizing taking into consideration that azaindenes are well known as an anti-fogging agent or a stabilizing agent among those skilled in the art, i.e., such afact could not be anticipated at all from the conventional common knowledge that in general antifogging or stabilizing agents reduce the sensitivity though they have the action of depressing fogging as is described above.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material comprising a support having thereon a silver halide emulsion layer containing at least one compound having a l,2-dithiolane ring or a 1,2-dithiane ring (hereinafter referred to as "compound A) and at least one of triazaindenes, tetrazaindenes or pentazaindencs.

:which have at least one hydroxy group (hereinafter referred to as compound B).

As preferred examples of compound A used in the invention, there are illustrated the compounds represented by the following formula;

dHnm-bu- X) r 11 (I) wherein X represents a divalent (hydrocarbon) rcsidue having 1 6 carbon atoms, R represents a carboxylic acid group, a carboxylic acid salt group, a carboxylic acid ester group. or a carboxylic acid amide group, m represents 2 or 3. and n represents 0 or 1.

As prefered examples of X in general formula (I), there are methylene, ethylene, propylene, hutylene. hexylene, etc.

As examples of prefered carboxylic acid salts there are alkali metal salts (e.g., sodium salts, potassium salts, etc.), alkaline earth metal salts (e.g., calcium salts, barium salts, etc.), ammonium salts, amine salts (e.g., methylamine salts, ethylamine salts, ethanolamine salts, etc.) and the like. The salts used are, of course, cation salts with the carboxylic acids.

Examples of preferred carboxylic acid esters are esters with 'a C C alkyl group or a phenyl group, and the like.

Examples of preferred carboxylic acid amides are carboxylic acid amide and carboxylic acid amide substituted by a C C alkyl group or by a phenyl group. and the like.

Additionally, in the above-illustrated general formula (I), when m represents 2, a dithiolane ring is formed and, when m represents 3, a dithiane ring is formed.

Compound A used in the invention is structurally characterized by containing a dithiolane ring or a dithiane ring, and exerts the action of lowering fogging of silver halides due to this structural feature. Therefore, compound A used in the invention is not particularly limited to that represented by the foregoing general formula (I). and any compound having a dithiolane or a dithiane ring may be used.

The compounds represented by the foregoing general formula (I) may be synthesized according to known processes, e.g., described in "Journal of the American Chemical Society," 76, pp. 1,828 1832 (1954).

The following are typical compounds represented by general formula (I) useful in the present invention.

A-l S S H2 0 11-0 0 O H l,2-Dithiolane-3methanoie acid A-2 s -s H2O CH-C O O K Potassium 1,2-dithiolane-3-methanoate H O GH(CH2)a-COOH Wow Hifi-PEPEPk tfi-YQ:PEEEQE A-4 S S H O CH(CH COONa Sodium 4-(1,2-dithto1an-3-yl)-butanoate A-5 S S Hi0 OH''(CH2)4 COOH 5(1,2-Dithlolan-3-yl)-pentanoic acid A4; S S

11,0 OH-(CH2)4COOH-N NC H OH 5-(1,2-Dithiolan-3-yl)-pentanoie acid monoethanolamine salt A-7 s-s HC\ CH(CH2)4COON&

Sodium 5-(1,2-dithiolan-3-yl)-pentanoate A -8 S S 112C CI'L-(OHgh-COONHd Ammonium 5-(1,2-dithi0lan-3-yl)-pentanoate A-J S S H2C\ CH(OH2)i-COOH-H2NCHs 5-(1,2-Dithiola.n-3-y1)-pentanoie acid methylamine salt A-lO S S H2C\ CH(CHg)4COOCH:

Methyl 5-(l,2-dithiolan-3-yl)-pentanoate A-ll S S H CH(CH2)4CONH2 5-(1,2-Dithiolan-3-yl)-pentanoic acid amine Potassium 4-(l,2-dithian-3 -yl)-butan0atc Compound B used in the invention includes triazaindenes. tetrazaindenes and pcntazaindenes which have at least one hydroxy group attached to a carbon atom which forms the azaindene ring. The preferred substitution point(s) for the OH group(s) is the 5- and/or 7- position on the azaindene ring. but this is not limitative. These compounds may further contain substituents in addition to the hydroxy group, and such are included within the terms triazaindcnes, tetrazaindenes and pentazaindenes in the specification and claims. As specific examples of such substituents. there are illustrated a halogen, an alkyl group having 1 17 carbon atoms, an aralkyl group, an aryl group, an alkoxy group having I 18 carbon atoms, a carboxyl group. an alkoxycarbonyl group having 1 18 carbon atoms, an aminocarbonyl group, a cyano group, a group forming a hydrocarbon ring together with the adjacent carbon atoms (See for example, compounds 8-1 2, 8-14, where a saturated ring is formed; the adjacent carbon atoms are bicinal carbon atoms which form the azaindene ring), and the like.

in the present invention, the presence of any special substituent(s) on the azaindene ring other than the hydroxy group is rather immaterial and any substituent(s) excepting those such as a nitro group or mercapto group which adversely affect the photographic properties, such as sensitivity and fog, of the light-sensitive emulsion can be present. All such substituted azaindenes are to be construed as within the scope of the present invention.

Compound B is characterized by containing an azaindene ring having at least one hydroxy group, and may contain substituents other than are described above.

Compound B may be synthesized according to known processes, e.g.. described in "Chemical and Pharmaceutical Bulletin, 6, pp. 583 586 (1958), or ibid., 10, pp. 612 620 (I962).

Typical useful examples of compound 8 are as follows.

13-3 cm 13-15 on N/N M/ f yaa H 5 7 CH3 \N \N B's HO 13-18 (|)H N 20 /N N 3'7 05H /N\%N\ t \AN N I \N/ B 10 m an. /N a}: HO-

13-20 Ho //N r H l l 13-9 HO N N \(N 1 03 E000 N\N/ The amounts of compound (A) and compound (B) H added vary depending upon the presence of additives B 0H 3 to the emulsion, such as a sensitizing agent. In general. greater amounts of a sensitizing agent causes higher fog 13502000 N 40 density, thus, greater amounts of the compounds are needed. In general. compound (A) is suitably added in x an amount of from about 0.0005 g to about 5 g and N compound (B) from about 0.005 to about g. per 1 0NH2 mol of silver halide contained in the emulsion. Prefera- B-11 OH bly. compound (A) is added in an amount of from ,N about 0.005 to 0.5 g, compound (B) from about 0.05 13502000 to 5 g. same basis as above. The optimal amount can be J determined by the preliminary test well known by those 50 skilled in the art, i.e.. a series of runs, wherein the N amount of the compounds is varied. B42 OH As will be appreciated by one skilled in the art. one A can use one or more different compounds (A) in combination with one or more different compounds (8 In H this case of course, the total amount of the different \N compounds suitably falls within the ranges recited above. CH3 N These compounds are added to a silver halide emul- N sion advantageously as a solution. As a suitable solvent, I organic solvents which exert no detrimental effect on a photographic emulsion, such as lower alcohols and H H2- ketones, as well as water. can be used. BM 0H In general. a silver halide photographic light-sensitive material is produced via the following steps; l prepa- Nx ration and weighing of starting materials for the pro- H duction of emulsion; (2) emulsification; (3) first ripening or physical ripening; (4) removal of water-soluble N N salts; (5 second ripening or chemical ripening; and (6) coming of the emulsion. (For example, see Making and Coating Photographic Emulsions, pp. 17 22, issued by Focal Press Co.)

According to the present invention, compound (A) and compound (B) may effectively be added to an emulsion during production of the silver halide emulsion (i.e., in the above-described steps (1) to or immediately before coating the emulsion. A particularly prefered stage of the addition is between the second ripening step and the coating step.

As the silver halide for the photographic emulsion in the present invention, any of the ,known ones such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chloroiodide, silver chlorobromoiodide and the like can be used. in addition, halogen conversion-type silver halide grains as described in British Pat. No. 635,841 may also be used effectively.

As the binder for the silver halide, any hydrophilic colloid applied to usual silver halide emulsions may be used. For example, gelatin, albumin, gum arabic, agaragar, cellulose derivatives (e.g., carboxycellulose alkyl esters, hydroxyethyl cellulose, carboxymethylhydroxyethyl cellulose, etc.), synthetic resins (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, etc.), and the like are merely a small sampling of those hydrophilic colloids which can be used in the present invention.

The generally used ratio of silver halide binder is l 2 about from 0.1 to 20. A preferred particle size for the silver halide is from about 0.05. to about 5 microns. Neither of these ranges are limitative, and they can be varied in a manner known to the art.

To the photographic emulsions used in the invention may be added, in a manner known to the art, compounds containing group 1 elements such as rubidium, cesium, copper, silver, gold, etc., group 1] elements such as magnesium, strontium, zinc, cadmium, mercury, etc., group Vlll elements such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, irid- ,ium, platinum, etc., in order to adjust the photographic characteristics of the emulsion.

Also, the photographic emulsion can be subjected to chemical ripening with active gelatin or with the use of a sulfur compound in a manner as described in U.S. Pat. Nos. 1,574,944; 1,623,499 or 2,410,689.

' The photographic emulsion can be chemically sensitized with gold salts such as are described in U.S. Pat. No. 2,399,083; with reducing agents such as the stannous salts described in U.S. Pat. No. 2,487,850; reducing agents such as the polyamines described in U.S. Pat. No. 2,52l,925; with bis(beta-aminoethyl)sulfides and the water-solublesalts thereof described in U.S. Pat. No. 2,521,926; with compounds containing a labile selenium atom as described in U.S. Pat. Nos. 3,297,446; 3,297,447 and 3,442,653; can be sensitized by the addition of polyalkylene glycols as described in U.S. Pat. Nos. 2,423,549 and 2,441,389; or with various derivatives of alkylene oxides as described in U.S. Pat. No. 2,240,472 and British Pat. No. 443,559.

- The above-described photographic emulsion may, of course, be spectrally sensitized with a cyanine or merocyanine dye.

The hydrophilic colloid used in the photographic light-sensitive material of the invention is advantageously hardened by the generally used hardeners of the aldehyde series, methylol series, 1,4-dioxane series,

' aziridine series, isoxazole series, carbodiimide series,

genta dye-forming couplers of the pyrazolone series,

indazolone series, etc., can advantageously be used. In addition, all of the cyan dye-forming couplers of the phenol series, naphthol series, etc.,can advantageously be used. These couplers may contain a coupling-off group at the active carbon atom positioned at the coupling cite. Those couplers rendered nondiffusible with a ballast group are prefered. With respect to these couplers, a great number of ballasted compounds are well known.

These dye-forming couplers can be dispersed in a hydrophilic colloid in any known manner. They can advantageously be dispersed with the use of a coupler solvent as described in U.S. Pat. No. 2,322,027, etc.

The photographic light-sensitive material of the invention can contain aplasticizer such as glycerin, a coating aid such as saponin, polyethylene glycol monolauryl ether, etc., a lubricating agent such as a silicone resin, paraffin, etc., a matting agent such as starch, titanium dioxide, a silicate, etc., a water-soluble azo dye, polymethine dye, diphenylmethane dye, etc., a brightening agent of the stylbine series, triazine series, oxazole series, coumarin series, etc., antistatic agents such as the ionic polymers described in U.S. Pat. No. 2,861,056, and antioxidants such as hydroquinone derivatives, ascorbic acid, etc. I

In addition, the photographic light-sensitive material of the invention can contain ultraviolet ray-absorbing agents such as Michlers diketone sulfonic acid, benzotriazole, etc., or may contain colloidal silver, carbon black or the like to prevent static marks.

As the support advantageously used in the photographic light-sensitive material of the invention, there are cellulose ester films such as cellulose nitrate. cellulose acetate, etc., polyester films such as polyethylene terephthalatefilms, etc., polyvinyl chloride films, polystyrene films, polycarbonate films, baryta paper and albisulfite, bromide, iodide, etc. of an alkali metal. Other useful black-and-white developing agents are described, for example, in The Theory of the Photographic Process, 3rd Edition, pp. 278 331, issued by MacMillan Co.

Color developers as are commonly used in the art can also be used in the present invention, i.e., any alkaline aqueous solution containing a color-developing agent. As the color-developing agents, all known dye-forming aromatic primary. amine developers such as phenylenediamines (e.g., N,N-diethyl-p-phenylene-diamine, N-

0.01 percent aqueous potassium chloroaurate solution minutes.

After the completion of ripening, the resulting emul- EXAMPLE 1' Tol,000 g of a light-sensitive gelatino silver bromoiodide (1.2 mol percent iodide) emulsion (containing 0.8 mol silver) having an average silver halide diameter of 1.0 micron there were added 30 ml of 0.01 percent aqueous sodiuir thiosulfate solution and 15 ml of a y yd yet yl-p-p y e ediaminc. N-ethyl-N- sion was divided into three equal portions, one ofwhich hydroxyethyl-2-methyl-p-phenylenediamine, Nethylwas used as a control and to the remaining two of which beta-N-methanesulfonamidoethyl-3-methyl-4- were added, respectively, the compounds described in aminoaniline, N,N-diethyl-2-methyl-p- Table 1. Each ofthe thus obtained three emulsions was phenylenediamine, and the sulfonates, hydrochlorides applied to a triacetate cellulose film support in a coated and sulfites thereof, etc.) can be used. The color develsilver amount of 2.5-X 10 mol/m then dried. oper may further contain generally used additives such The thus prepared samples were subjected to sensias a sulfite, carbonatebisulfite, bromide or iodide of an me ry in a known m e to mp r Ihc sensitivity. alkali metal, benzyl alcohol and the lik gamma value and fog density of each sample. Develop- 0 As other processing solutions, e.g., a bleaching solumehl was Conducted at Q C for 3 mlhulcs 115mg tion, a fixing solution, a stabilizing solution, etc., ones P having the following chmphslhhhknown in the art may advantageously be used. These processing solutions may be used in combinations of N Mcthy| p umwhen, mm 21 g two or more of them, e.g., as a bleach-fixing solution, Hydroquinonc 8.8 g a fix-stabilizing solution or a bleach-fixstabilizing solu- Anhydmu h 9 Anhydrous sodium carbonate 48.0 g tlon- Potassium bromide 5.0 g Such solutions are well known in the art, and any of Water 10 make 1 liter such known solutions are useful. Ableaching solution contains a silver oxidizing agent(s), e.g., water-soluble Aftehdeveloplhehh each the samples "hferricyanides, a 'simple water-soluble ferric, cupric or mersed m a hpp bath at 20 C lzpercehf "101d b l i Salt d Complex Salts f an lk li metal d 25 aqueous solution) for seconds, washed for l minute polyvalent cations with an organic acid. Typical examwith a Fuhhlhg which h 111 h 8 minutes ples of the polyvalent cations are ferric ions, cobaltic u ng a fixing solution having the following composiions, cupric ions, etc. Typical examples of the organic h Washed for 5 minutes wllh ruhhlhg which and acids are ethylene diamine tetraacetic acid, nitrilotridriedacetic acid, etc. A fixing solution contains a silver hal- 30 ide solvent(s) for example, a water-soluble thiosulfate,

h. A t b. r l t. Sodium thiosultiitc n -50 g I watersoluble t iocyanate etc. 5 a 1 ze so u ion Anhydrous 15 g contains, of course, a stabilizer such as formaldehyde, gorichacild i: g otas auni l, g citr c acid, etc. Specific examples of these compounds Sodium mum m g 3T0 illustrated on U.S. Pat. NO. 3,582,322. Water to make l liter.

In the silver halide emulsion in accordance with the present invention containing compound A and com- In addition, the three samples were subjected to an pound B, fogging alone is lowered without a reduction incubation test. After leaving each sample at C and in sensitivity or the gamma value. In addition, the emulat percent RH for 48 hours in the unexposed state, sion has the feature that less fog is formed and varia- 40 they were exposed and developed in the same manner tions in sensitivity and the gamma value are lessened as in the case ofthe fresh samples. The results obtained during storage. are shown in Table I.

TABLE 1 Com- Added Fresh lncubated pound amount of compound Relative Fog Relative Fog amma amma per I mol sensisensiof silver tivity tivity Control None 100 1.20 0.12 115 0.75 0.18 A s 65 1.00 0.08 70 0.82 0.09 A 5 65 98 1.18 0.08 1.22 0.07 B 3 350 The present invention will now be described in As is evident from Table 1, although compound A greater detail by several non-limiting examples of prehas the effect of lowering fogging, it reduces both the ferred embodiments. 60 sensitivity and gamma at the same time. On the other hand, when compound A and compound B are used in combination, fogging can be prevented without reducing sensitivity and gamma. In addition, almost no variations in the photographic characteristics were observed under the conditions of high temperature and high humidity, and thus, it can be seen that the sample in accordance with the invention has an extremely stable prescrvability.

EXAMPLE 2 A silver halide gelatin photographic emulsion (containing 0.06 mol silver per 100 g) comprising silver excellent preservability is shown,

EXAMPLE 3 chlorobromide containing 25 mol percent chlorine sub- 5 A silver halide gelatin photographic emulsion (conjected to second ripening with the use of sulfur comtaining 0.08 mol silver per 100 g) comprising silver bropound and gold salt was prepared in the same manner moiodide'containing 1.8 mol percent iodide was preas in Example 1. pared by conducting second ripening with the use of After the completion of ripening, the resulting emulthe sulfur compound and gold salt in the same manner sion was divided into 4 equal portions. One of them was as m EXamPle 1 and adding 0.4 g. P 1 m l e used as a control, and to the remaining 3 portions were P y y g y (mean molecular weight added, respectively, the Compounds describ d i T bl to sensitize the emulsion. The resulting emulsion was 2. Each of the resulting 4 emulsions was applied to a dlvlded three equdl P Of h W115 paper Support h i mated on h Sides th f used as a control, and to the remaining 2 portions were polyethylene containing dispersed therein white titaadded, P Q Y the Compounds Show" Tllblc nium dioxide, in a coated silver amount of 1.9 X 10 Thereafter, film Samples were P p according to mol/m then dried. Example The thus prepared samples were subjected to sensi- Each ofthe Samples was subficted to f l y tometry in a known manner to compare the sensitivity, a known manner compdfe the sensltlvltygamma gamma value and fog density of each Sample Develop value and fog dens ty, sub ected to development at mem was conducted at for 2 minutes using a 20C for 10 minutes in a developer having the following veloper having the following Composition composition, and subsequently processed in the same manner as in Example 1.

N-Methyl-p-aminophenol sulfate 3.1 g I Hydroquinone 12,0 g N-Methyl-p-aminophenol sulfate l.5 g Anhydrous sodium sulfite 45.0 g Hydr quin n 1.3 g Anhydrous sodium carbonate 67.5 g Anhydrous sodium i c 75.0 g Potassium bromide 1 9 g Borax 4,5 g Wat r t mak 2 Potassium bromide (1.4 g

Water to make 1 liter.

After development each of the Samples was pro- Also with res ect to each sam le an inc bationt st cessed in the same manner as in Example 1. Also, an was conducted the Same as i I incubation test was conducted accordingto Example 1. X p e The results are shown in Table 3. It can be seen therein The results obtained are shown in Table 2.

that excellent photographic characterlstlcs can be obtained by the combined use of compound A and compound B.

TABLE 2 Com- Added Fresh incubated pound amount of compound Relative Fog Relative Fog amma amma per 1 mol sensisensiof silver tivity tivity Control None 100 2.85 0.06 2.10 0.07 A 11 2.40 0.04 60 2.10 0.06 A 11 140 55 2.00 0.02 45 2.15 0.04- A 11 70 98 2.80 0.03 98 2.35 0.03 B- 3 380 TABLE 3 Com- Added Fresh lncubated pound amount of 1 compound Relative Fog Relative Fog amma amma per 1 mol sensisensiof silver tivity tivity Control None 100 1.08 0.17 65 0.86 0.22 A 12 74 65 0.92 0.12 55 0.75 0.15 A-12 74 98 1.10 0.12 101 1.12 0.13 B 5 420 is l at f om Table 2, the combined use of com- AS EXAMPLE 4 pound A and compound B enables one to remove the defect of the compound A and lowers fogging while A fine-grained silver chlorobromide photographic emulsion (average grain size was 0.25 microns; containing 0.08 mol silver per 100 g) containing 35 mol percent chloride was prepared and subjected to a second ripening in the same manner as .in Example I.

described in Production of Motion Pictures in Color UsingEastman Color Films, Ill-l5 to Ill-26, published by Eastman Kodak.

The incubation test was conducted in the same man- Thereafter, the resulting-emulsion was speetrally sensi- 5 ner as in Example 1. The results obtained are shown in tized by adding the speetrally sensitizing dye repre- Table 4. Thus, it can be seen that, in a color photosented by the following formula so that sensitization graphic emulsion also, excellent photographic characmaximum would be at about 555 mp. (0.1 percent teristics can be obtained by the combined use otcomrnethanolsolution of t he sensitizing dye was added in pound A and compound B.

TABLE 4 Com- Added Fresh lncubated pound amount of compound Relative Fog Relative Fog amma amma per l mol sensi sensiof silver tivity tivity Control None l 2.80 0.09 75 2.34 0J2 A4 I 34 62 2.02 0.05 68 2.13 0.06 A 5 34 98 2.70 0.05 95 2.75 0.05 B 3 680 an amount of 8 ml per l00 g of emulsion). EXAMPLE 5 To fine-grained high contrast silver chlorobromo- 02m iodide emulsions (average grain size was 0.6 microns) J containing 1.2 mol percent silver iodide and 8.2 mol percent silver chloride having been subjected to second g ripening with the use of the sulfur compound and gold (gsmsor salt in the same manner as in Example I were added the 03H; compounds described in Table 5, then a dispersion of L 5 a gelatin aqueous solution containing dispersed therein Dali-N H20 as a yellow dye-forming coupler alpha-(2- methoxybenzoyl)-2-chloro-5-[alpha-(2,4-di-t- The thus speetrally sensitized emulsion was divided into 3 equal portions. One of them was used as a control. To the remaining 2 portions were added, respectively, the compounds shown in Table 4. Then, a dispersion of gelatin aqueous solution containing dispersed therein as a magenta dye-forming coupler, l- (2,4,6-trichlorophenyl)-3- 3-[alpha-(2,4-di-tamylphenoxy)-butylamido[benzamido -5- pyrazolone(dibutyl phthalate solution) was added to the three emulsions toprepare coating solutions (8 g of magenta coupler per 100g of emulsion was added). Each of the resulting coating solutions was applied to a cellulose triacetate film support in a coated silver amount of 9.8 X l0" mol/m then dried. The thus prepared samples were subjected to sensitometry in a known mannerto compare sensitivity, gamma and fog density. The samples were processed through the pro cessing baths of color development, stopfixing, bleaching and fixing selected from among the processing steps amylphenoxy)butylamido[-acetanilide(dibutyl phthalate solution) was added thereto to prepare coating solutions (6.5 g of yellow coupler per 100 g of emulsion was added). The resulting coating solutions were applied to the same paper support as was used in Example 0 2 in a coated silver amount of 5.9 X 10"" mol/m then dried.

Thethus prepared samples were subjected to sensitometry in a known manner to compare sensitivity, gamma and fog density. The samples were processed according to processing step B for color photographic paper described in Example 2 in US. Pat. No. 3,582,322.

An incubation test was conducted in the same manner as in Example l. The results obtained are shown in Table 5. It can be seen that in this case also fogging alone can be lowered by the combined use of compound A and compound B while maintaining the sensitivity and gamma value, and the photographic characteristics upon storage are extremely stable.

TABLE 5 Com- Added Fresh lncubated pound amount of compound Relative Fog Relative Fog arnma amma per l mol sensisensiof silver tivity tivity Control None [00 2.43 (H2 105 2.01 0.15 A ll 57 72 2.15 0.08 2.20 0.09 A ll 57 2.40 0.08 98 2.45 0.08 B 5 335 While the invention has been described in detail and with reference .to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departingfrom the spirit and scope thereof.

What is claimed is: I I

y l. A photographic material comprising a support having thereon a silver halide emulsion layer containing (1) at least one of a triazaindene, a tetrazaindene' or a pentazaindene having at least one hydroxy group wherein X represents an alkylene group having 1-6 carbon atoms, R represents a carboxylic acid group, a carboxylic acid salt group, a carboxylic acid ester group,

or a carboxylic acid amide group, m represents 2 or 3, and n represents Oor l.

2. A photographic material as described in claim 1 wherein said silver halide emulsion is sensitized by at least one chemical sensitizing agent from the group: a sulfur sensitizing agent, a noble metal sensitizing agent, a reduction sensitizing agent or a selenium sensitizing agent.

3. A photographic material as described in claim 1 where the total amount. of the (l) at least one of the triazaindene, tetraazaindene and pentazaindene is about 0.005 to about 50 g and the (2) total amount of the at least one of a compound having a 1,2-dithiolane ora l,2-dithiane ring is about 0.0005 g to 5 g, per 1 mol of silver halide in the silver halide emulsion.

4. A photographic material as described in claim 3 where the total amount of l) is about 0.05 to 5 g and the total amount of (2) is about 0.0005 to 5 g, per 1 mol of silver halide in the silver halide emulsion.

5. A photographic material as described in claim 1 where in the general formula X is an alkylene group from the series methylene to decylene, when R is an carboxylic acid ester the ester is with a C C alkyl group or a phenyl group and when R is a carboxylic acid amide it is an amide per se or substituted with a C, C alkyl group or a phenyl group.

6. A photographic material as described in claim 1 where the triazaindene, tetraazaindene or pentazaindene issubstituted with a C, C, alkyl, aralkyl, aryl, C, C,,, alkoxy, carboxyl, C, C alkoxycarbonyl, aminocarbonyl, cyano or a group forming a hydrocarbon ring with adjacent carbon atoms in the azaindene ring.

7. A photographic material as described in claim 1 where said compound is '8. A photographic material as described in claim 1 rh ra aissqm aqp s.

9. A photographic material as described in claim I where said compound is S v v HZC/ s HA3 10. A photographic material as described in claim I where said azaindene is 11. A photographic material as described in claim 1 where said azaindene is on, Y

on l

12. A photographic material as described in claim 1 where said compound is and said azaindene is 13. A photographic material as described in claim 1 where said compound is and said azaindene is N N CH3 N 14. A photographic material as described in claim 1 where said compound is 7 H2 and said azaindene is 15. A photographic material as described in claim I and said azaindene is where said compound is C OII 

1. A PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT HAVING THEREON A SILVER HALIDE EMULSION LAYER CONTAINING (1) AT LEAST ONE OF A TRIAZAINDENE, A TETRAZAINDENE OR A PENTAZAINDENE HAVING AT LEAST ONE HYDROXY GROUP AND (2) AT LEAST OF A COMPOUND HAVING A 1,2-DITHIOLANE RING OR A 1,2-DITHIANE RING REPRESENTED BY THE FORMULA:
 2. A photographic material as described in claim 1 wherein said silver halide emulsion is sensitized by at least one chemical sensitizing agent from the group: a sulfur sensitizing agent, a noble metal sensitizing agent, a reduction sensitizing agent or a selenium sensitizing agent.
 3. A photographic material as described in claim 1 where the total amount of the (1) at least one of the triazaindene, tetraazaindene and pentazaindene is about 0.005 to about 50 g and the (2) total amount of the at least one of a compound having a 1,2-dithiolane or a 1,2-dithiane ring is about 0.0005 g to 5 g, per 1 mol of silver halide in the silver halide emulsion.
 4. A photographic material as described in claim 3 where the total amount of (1) is about 0.05 to 5 g and the total amount of (2) is about 0.0005 to 5 g, per 1 mol of silver halide in the silver halide emulsion.
 5. A photographic material as described in claim 1 where in the general formula X is an alkylene group from the series methylene to decylene, when R is an carboxylic acid ester the ester is with a C1 - C12 alkyl group or a phenyl group and when R is a carboxylic acid amide it is an amide per se or substituted with a C1 - C12 alkyl group or a phEnyl group.
 6. A photographic material as described in claim 1 where the triazaindene, tetraazaindene or pentazaindene is substituted with a C1 - C17 alkyl, aralkyl, aryl, C1 - C18 alkoxy, carboxyl, C1 -C18 alkoxycarbonyl, aminocarbonyl, cyano or a group forming a hydrocarbon ring with adjacent carbon atoms in the azaindene ring.
 7. A photographic material as described in claim 1 where said compound is
 8. A photographic material as described in claim 1 where said compound is
 9. A photographic material as described in claim 1 where said compound is
 10. A photographic material as described in claim 1 where said azaindene is
 11. A photographic material as described in claim 1 where said azaindene is
 12. A photographic material as described in claim 1 where said compound is
 13. A photographic material as described in claim 1 where said compound is
 14. A photographic material as described in claim 1 where said compound is
 15. A photographic material as described in claim 1 where said compound is 